DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
www.acta.urk.edu.pl/pl ISSN 1644-0765
O R I G I N A L PA P E R Accepted: 04.11.2019
IMPACT OF DEFORESTATION ON CHANGES OF ION SHARE
IN CHEMICAL COMPOSITION OF WATERS OF THE MALINOWSKI
STREAM ALONG LONGITUDINAL HYDROCHEMICAL PROFILES
Amanda Kosmowska
Institute of Geography and Spatial Management, Jagiellonian University in Kraków, ul. Gronostajowa 7, 30-387 Kraków ABSTRACT
Aim of the study
The aim of the study was to determine the changes of ion share in chemical composition of water with the catchment area increase along longitudinal hydrochemical profiles in an area affected by an ecological di-saster.
Material and methods
The research was conducted in the Malinowski stream catchment in the Skrzyczne massif in the Silesian Beskid mountain range from 2013 to 2014. The catchment was divided into smaller sub-catchments (depen-dent and indepen(depen-dent) and 6 longitudinal profiles were separated along the catchment with the increase in the catchment area surface. Water samples were collected in catchments with a different deforestation level
on a monthly basis and its physical and chemical features (pH, EC25°C, Tw) were measured. The chemical
composition of water was determined with the ion chromatography method (DIONEX 2000) in the range of
14 ions (Ca2+, Mg2+, Na+, K+, NH
4+, Li+, HCO3–, SO42–, Cl–, NO2–, NO3–, PO43–, Br–, F–).
Results and conclusions
The conducted research showed the impact of deforestation on the ion share in the chemical composition of
water. In the deforested catchments, an increase in the share of SO42–, and a decrease in the share of HCO
3–
were observed. The share of SO42– in the waters that were draining the deforested catchment was so high that
it occured in the first position in the water’s hydrochemical type, while the concentration of HCO3– was so low
that its share was minimal. The analysis of hydrochemical types changes along longitudinal profiles showed the difference in chemical composition of waters draining the upper, deforested zone in comparison to the
lower, forested zone. As the catchment area increases, the importance of NO3– decreases and the importance
of HCO3– increases. If the research was conducted exclusively in the profile that closes the Malinowski stream
catchment it would show that the catchment is a typical Carpathian catchment in hydrochemical terms, where bicarbonates are in the first place in water chemical composition. The analysis of water chemical composition conducted in the longitudinal profiles enables the identification of hydrochemical effects of the degradation of forest stand in mountain catchment.
Keywords: stream water chemistry, deforestation, acidic atmospheric deposition, concentration of NO3– and
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
98 www.acta.urk.edu.pl/pl
INTRODUCTION
The chemical composition of stream waters in catch-ment according to Macioszczyk (1987), Pazdro and Kozerski (1990), Chełmicki (2012) is determined by an array of environmental factors. National factors such as geological structure, susceptibility to weath-ering and leaching, total precipitation play a dominant role. Also, it is strongly influenced by vegetation and plant root systems that, on one hand, collect water from the system, and on the other, change physico-chemical conditions of the soil layer (or ground and residual soil layers), and promote the passage of chemical ingredients into soil solution. Even minor surface changes in terms of land use conditions (e.g. deforestation) in seepage spring area can strongly in-fluence water’s chemical composition (Czop et al., 2008). Today, in the period of a growing anthropo-pressure, human economic activity plays increasingly important role (Chełmicki, 2012). Atmospheric pol-lution has a negative impact on forest ecosystems as it is a direct cause of acid rainfalls (Bytnerowicz et al., 2002; Małek et al., 2005), it disturbs the natural chemistry of precipitation, surface and underground waters as well as soil (Małek and Gawęda, 2006a, 2006b; Małek, 2010; Borg and Sundbom, 2014). In the Silesian Beskid range it was shown that strong an-thropopressure led to dying of forest stand in moun-tain areas (Małek and Krakowian, 2012; Kosmowska et al., 2016), and aggradation of sulphur and nitrogen compounds may cause disturbances in proper func-tioning of water and land ecosystems (Moldan and Schnoor, 1992; Borg and Sundbom, 2014).
The aim of the study was to determine the chang-es of ion share in chemical composition of water with the catchment area increase along longitudinal hydro-chemical profiles in an area affected by an ecological disaster of dying of spruce.
RESEARCH SITE
The research on changes in a chemical composition of waters was conducted in the Malinowski stream catchment . The catchment is located in the Skrzyczne massif, the highest peak (1257 m a.s.l.) in the Silesian Beskid range. It is designated by the side ridge of the Skrzyczne massif, which stretches southwest through
Małe Skrzyczne (1211 m a.s.l.), Kopa Skrzyczańska (1189 m a.s.l.) up to Malinowska Skała (1152 m a.s.l.) (see: Fig. 1). In terms of physical and geographical regionalisation, the area belongs to the Western Car-pathians province, the Outer CarCar-pathians sub–prov-ince, the Western Beskid macroregion and the Silesian Beskid mesoregion (Balon and Jodłowski, 2014).
These mountains were uplifted during the Al-pine orogeny in the late Paleogene and the Miocene (Oszczypko, 1995). The glaciation that occurred in the Quaternary had a great impact on the relief of the area. As a result of intensive periglacial processes, charac-teristic gentle slopes and peaks formed that are inter-sected by deep valleys. The current landform of the Silesian Beskid is formed mainly as a result of water erosion. Landslides on slopes and valleys, which are the result of undercutting slopes by water erosion, play a major role in the evolution of the landform (Małek and Gawęda, 2004). Mountain ranges of the Silesian Beskid are formed of the Godula sandstone with a low content slates (Alexandrowicz, 1999; Geologiczna Mapa Polski 1:50000 1966a, 1966b).
This area is covered with a forest stand charac-terised by a high share of the Istebna spruce that grows mainly in monocultures (Barszcz and Małek, 2015). This spruce, however, is not a native species in the Silesian Beskid, hence its share in natural forest stands was low in the past. In the 18th century, along with the increase in the development of industry and agriculture, robbery of wood resources (beech and sycamore) increased. Natural lower subalpine forests were destroyed and replaced with monocultures of spruce of foreign origin, which with time began to disintegrate (Małek, 2015). The main reason for the dying out of forest stands in the research site was the bad condition of forest caused by the immission of industrial pollution from the Czech Republic and the Silesian–Cracow agglomeration. The dying out con-cerned mainly forests located in the ridge parts of the highest hills, most exposed to weather conditions (Capecki, 1994; Kosmowska et al., 2016; Małek et al., 2012a, 2012b).
The Malinowski stream catchment is limited by a stream gauge of the Polish Institute of Meteorolo-gy and Water Management (IMGW) in Lipowa, and it was monitored by the IMGW until 1983. In the 1974 to 1983 hydrological decade, the average discharge of the
Malinowski stream was 0.64 m3 ∙ s–1 and ranged from
Qmin = 0.04 m3 ∙ s–1 11.11.1983 r. to Qmax = 12.4 m3 ∙ s–1
20.01.1974 r. (Hydrologiczny rocznik wód powierzch-niowych, 1974–1983). Average annual rainfall in the Silesian Beskid is 1400 mm and average annual air temperature in the lower subalpine forest is 5.6°C. The
average duration of the growing season is 192 days (Durło, 2012).
The Malinowski stream catchment has an area of 21.39 km2. Sub-catchments located in the upper, ridge
forest zone are independent and are characterised by a small area not exceeding 0.1 km2. These catchments
Fig. 1. Study area – Malinowski stream catchment 1 – independent catchments closing profiles, 2 – dependent catchments closing profiles, 3 – peaks, 4 – catchment boundaries, 5 – streams, 6 – young forest, 7 – high forest, 8 – deforested area
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
100 www.acta.urk.edu.pl/pl
are the most deforested, from 1.3% of the forest cov-er in catchment no. 2 to 52.0% in catchment no. 1. Catchment no. 4 is deforested in 85.3% and is current-ly covered by young forest. Catchments (dependent and independent) located in the middle forest zone are characterised by a larger area ranging from 0.34 km2
to 1.62 km2 and much greater afforestation ranging
from 44.2% to 85.9%. Catchments located in the low-er forest zone are mostly dependent and they limit hy-drochemical systems. They cover area ranging from 1.63 km2 to 21.9 km2, and their ranges from 57.1% to
69.9% (see: Table 1). Table 1. Characteristics of sub-catchments of the Malinowski stream
Forest zones ID catchmentType of Area
Forest cover
Average slope
Young forest High forest Total
[km2] [%] [%] [%] [o] Upper 1 I 0.09 13.9 38.1 52.0 15.9 2 I 0.03 1.2 0.1 1.3 15.4 3 I 0.04 27.1 22.9 50.0 12.9 4 I 0.05 12.8 1.9 14.7 24.2 Middle 5 I 0.34 3.7 40.5 44.2 9.9 6 D 1.00 7.1 41.0 48.1 7.6 7 D 1.39 22.5 47.1 69.6 9.2 8 D 1.13 37.8 32.8 70.6 7.8 9 D 1.62 19.2 48.3 67.5 8.2 10 I 1.00 2.1 83.8 85.9 7.3 Lower 11 I 10.60 7.1 50.0 57.1 21.0 12 D 1.63 8.5 61.4 69.9 20.7 13 D 3.31 11.1 49.9 61.0 20.5 14 D 4.79 16.8 44.2 61.0 19.7 15 D 7.12 15.3 49.5 64.8 19.9 16 D 8.36 12.2 56.3 68.5 18.6 Malinowski Potok 17 D 21.39 8.2 54.6 62.8 15.1
Data source: own research – completed table (Kosmowska et at. 2016).
RESEARCH METHODS: FIELD, LABORATORY AND DATA ANALYSIS
Field methods
In order to determine the impact of deforestation on changes of ion share in chemical composition of wa-ters in the Malinowski stream catchment, research was conducted from November 2013 to October 2014. The research was conducted in 17 sub-catchments of the Malinowski stream. In 7 independent catchments (I) (spring or divergent ones) and 10 dependent (D) (catchments partially covering areas of other
catch-ments) (Ozga-Zielińska and Brzeziński, 1994). In each catchment, the physical and chemical properties of the water were measured monthly with the Professional YSI PLUS multi–parameter meter (YSI Inc., USA): water temperature, conductivity (EC25°C) and pH, and a water sample was taken to determine the chemical composition (n = 204).
Laboratory methods
Physical properties and chemical composition of water were analysed in the Hydrological and Chemical Lab-oratory of the Institute of Geography and Spatial
Man-agement of the Jagiellonian University (IGiGP UJ). In order to verify the values of EC and pH obtained with YSI meter in the field, they were analysed again in the laboratory. Subsequently, water samples were fil-tered through a syringe filter with a PTFE membrane (0.45 μm) to prepare them for the chromatography anal-ysis. Chemical composition analysis of water samples was conducted with the ion chromatography method with the DIONEX ICS 2000 system (Dionex Corpora-tion, USA). 14 ions were determined in the range of: 1) main ions of: calcium (Ca2+), magnesium (Mg2+),
sodium (Na+), potassium (K+), bicarbonate ions
(HCO3–), sulphate (VI) (SO42–), chloride (Cl–);
2) biogenic compounds of: ammonium ions (NH4+),
nitrate (III) (NO2–), nitrate (V) (NO3–),
orthophos-phate (V) (PO43–);
3) microelements of: lithium ions (Li+), bromide (Br–),
fluoride (F–).
The correctness of chemical analyses was verified based on the analysis of certified reference materials (Trios–94 [batch number 306]) and with the ion balance method (PN–89/C–04638/02). A detailed description of the progress of the laboratory procedure and meth-odology is presented in the monograph by Żelazny (Czasowo–przestrzenna zmienność cech fizykochem-icznych wód Tatrzańskiego Parku Narodowego, 2012). For interpretation, the main ions and NO3– were
se-lected, and other ions (Li+, NH
4+, Br–, PO43–, NO2–, F–)
were ignored in table comparisons due to their low con-centration (often below detection limit) (see: Table 2).
Table 2. Ion detection limits [LOD]
Cation LOD Anion LOD
[mg · dm–3] [mg · dm–3] Ca2+ 0.005 HCO 3– 0.025 Mg2+ 0.005 SO 42– 0.01 Na+ 0.01 NO 3– 0.0025 K+ 0.005 NO 2– 0.0025 NH4+ 0.005 Cl– 0.0025 Li+ 0.005 F– 0.001 Br– 0.005 PO43– 0.01 Data analysis
In order to determine the impact of deforestation on changes of ion share in chemical composition of water along longitudinal hydrochemical profiles:
– 6 longitudinal profiles (I, II, III, IV, V, VI) were de-signated along the catchment area (1–17) with the area increase. Profile I: 1–9–16–15–17, profile II: 2–7–13–14–15–16–17, profile III: 3–8–14–15–16– –17, profile IV: 4–6–12–13–14–15–16–17, profile V: 5–12–13–14–15–16–17, profile VI: 10–16–17; – for each sub-catchment, the degree of forest
co-verage, including young forest, and deforestation were calculated on the basis of aerial photographs taken in 2014;
– the average slope and catchment area were calcu-lated for each sub-catchment;
– the chemical composition of waters was interpre-ted due to the share of ions in the chemical com-position of water, expressed in (% mval · dm–3).
The share of ions was calculated assuming that the marked cations and anions constitute 100% of the chemical composition of water. It was assumed that anions and cations constitute 50% mval · dm–3
each so the total of anions = the total of cations. For the above assumption to be met, the spread of balance error was used (Ratajczak and Witczak, 1983 after: Witczak et al., 2013). The general mi-neralisation of waters was assumed as the total of determined ions;
– in order to present the synthetic chemical compo-sition of waters the commonly used in hydroche-mistry Szczukariew–Prikłoński classification was used (after: Macioszczyk, 1987). It assumes that the chemical features of natural waters are decided by 6 main ions (HCO3–, SO42–, Cl–, Ca2+, Mg2+, Na+)
share of which is not lower than 10% mval · dm–3,
and the name of a type starts with an anionic part in order from largest to smallest share. Due to the fact that the share of NO3– in chemical composition
of water sometimes exceeded 10% mval · dm–3,
NO3– was included in the classification and it was
written in the short name of the hydrochemical type in square brackets;
– the share of ions in the chemical compositions was expressed with hydrochemical types;
– the seasonal change of chemical composition of waters was defined based on two criteria:
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
102 www.acta.urk.edu.pl/pl
• time and volume of the share of NO3– in the
structure of the chemical composition, ex-pressed by the graph of the monthly coefficient of variation of the share of NO3– in the structure
of the chemical composition of water. It is the quotient of the monthly concentration of NO3–
(% mval · dm–3) to the average annual
concen-tration (Cmonth/Cannual avg.),
• the variability of the NO3– share marked with
the coefficient of variation (Cv) that expresses the ratio of the standard deviation to the aver-age, expressed as a percentage. The following criterion was adopted: Cv < 10% – equalised type, 10 < Cv < 20 – moderate type, Cv > 20 – non–equalised type;
– the chemical composition of stream waters was
cha-racterised with the following statistical measures: arithmetic mean, minimum and maximum value.
RESULTS OF THE STUDY General characteristics
Water courses draining the forested catchments of the Malinowski stream are characterised by a weak-ly alkaline reaction, while the water courses draining catchments located higher, closer to ridges, and that are more deforested, are characterised by higher acid-ification (lower pH) and belong to medium acid wa-ters [according to the division Pazdro and Kozerski (1990)]. In terms of mineralisation, these waters are low–mineralised and belong to so–called ultra–fresh waters (see: Table 3). Chemical composition analysis of waters draining forested and deforested catchments, show particularly large diversity within anions. SO42–
share in the chemical composition of waters draining independent, deforested catchments in the upper, ridge zone of the Skrzyczne massif is very large and that is
Table 3. Values of pH, electrical conductivity (EC25°C), mineral content (Mt) and coefficient of variation (Cv) in stream water
(n = 12)
Forest zones ID
pH EC25°C Mt
Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv
(pH) [%] [μS · cm–1] [%] [mg · dm–3] [%] Upper 1 6.33 6.49 6.57 1.0 43.8 47.3 51.1 5.1 27.67 31.45 35.25 6.8 2 5.71 5.81 5.98 1.5 38.3 40.0 41.8 3.0 21.86 23.91 25.83 5.7 3 6.28 6.45 6.55 1.5 44.2 49.3 52.8 5.1 29.38 35.16 41.04 9.7 4 7.04 7.14 7.37 1.4 59.2 74.3 82.8 8.6 46.93 53.69 58.04 6.1 Average value 6.34 6.47 6.62 1.4 46.4 52.7 57.1 5.5 31.46 36.05 40.04 7.1 Middle 5 7.14 7.37 7.59 1.7 73.1 83.6 91.8 7.3 56.29 61.22 67.65 6.3 6 7.05 7.25 7.38 1.2 62.1 74.2 91.2 10.3 47.21 53.92 65.85 9.4 7 7.28 7.38 7.54 0.9 74.2 83.5 88.8 5.2 56.13 61.29 68.00 7.0 8 7.09 7.23 7.33 1.0 59.0 64.8 71.5 5.2 42.75 47.06 56.72 8.4 9 7.09 7.22 7.34 1.1 65.5 73.1 78.0 5.4 46.41 52.22 57.50 6.7 10 7.15 7.32 7.56 1.6 59.3 69.8 81.2 9.5 39.95 51.44 61.99 11.9 Average value 7.13 7.30 7.46 1.3 65.5 74.8 83.8 7.2 48.12 54.53 62.95 8.3 Lower 11 7.06 7.37 7.56 1.9 64.6 76.2 82.2 6.3 51.78 56.75 65.41 7.4 12 7.17 7.26 7.36 0.9 66.3 78.1 85.3 7.2 50.20 57.41 64.03 6.9 13 6.89 7.30 7.49 2.3 48.4 77.2 85.3 15.0 40.98 56.86 65.66 13.3 14 6.93 7.26 7.52 2.4 47.6 74.5 93.4 14.7 41.76 55.06 63.03 11.4 15 6.65 7.25 7.49 3.2 41.4 73.8 90.0 15.9 34.34 53.27 60.00 12.9 16 7.11 7.31 7.54 1.6 66.9 76.2 88.3 7.5 49.77 55.11 61.06 7.0 Malinowski stream 17 7.18 7.35 7.55 1.3 67.0 76.5 81.5 6.0 50.62 56.19 62.99 7.3 Average value 7.00 7.30 7.50 1.9 57.5 76.1 86.6 10.4 45.64 55.81 63.17 9.5 Average total 6.89 7.10 7.28 1.6 57.7 70.1 78.7 8.1 43.18 50.71 57.65 8.5
20.72% mval · dm–3 on average, and in catchment no. 2
(almost totally deforested) is up to 31.58% mval · dm–3,
while in forested catchments in the middle and lower zone of the Skrzyczne massif it is much lower (avg. = 14.30% mval · dm–3 and avg. = 14.38% mval · dm–3).
Average share of NO3– in waters from ridge zone is
twice as high (avg. = 10.19% mval · dm–3) as in
for-ested catchments in the middle and lower zones (avg. = 5.42% mval · dm–3 and avg. = 4.62% mval · dm–3).
However, the average share of HCO3– in the chemical
composition of waters is almost twice as high in for-ested catchments (avg. = 28.32% mval · dm–3 and avg.
= 29.20% mval · dm–3) than in deforested catchments
(avg. = 16.59% mval · dm–3) (see: Table 4). Hydrochemical types
In terms of hydrochemistry, three–ion waters dominate in each of dependent and independent catchments, and they are described with the HCO3–SO4–Ca type
(n = 166; 81%). In the ridge zone, the hydrochemi-cal types of waters are more varied (n = 48). Four–ion waters of the HCO3–SO4–[NO3]–Ca type dominate (n = 23; 48%), next are three–ion waters of the HCO3– SO4–Ca type (n = 13; 27%) and some waters of the following types: SO4–[NO3]–Ca–Mg (n = 6; 13%), SO4–Ca–Mg (n = 3; 6%), SO4–[NO3]–Ca (n = 1; 2%), and two–ion waters of the SO4–Ca type (n = 2; 4%). In
the middle and lower catchment, waters of the HCO3–
SO4–Ca type dominate (n = 153; 98%). The HCO3–
SO4–[NO3]–Ca type (n = 1; 0,6%) was observed only
once in the middle zone, and in the lower the HCO3–
Ca type (n = 2; 1,4%) was observed twice (see: Ta-ble 5). The occurrence of this different hydrochemical type of water in the lower zone is probably related to the rapid, one–hour rainfall that occurred during the field research and water sampling.
Longitudinal profiles
Analysis of changes in the share of ions in the chem-ical composition of water shows that along the lon-gitudinal hydrochemical profiles two different phe-nomena can be observed: enrichment and depletion of water into single ions, which results in an increase or decrease in the share of some ions expressed in % mval · dm–3 in the chemical composition of water
in sub-catchments of the Malinowski stream. In the case of NO3–, a decrease of their share in the chemical
composition of water usually occurs, in the direction away from ridge catchments toward stream mouths (profiles: I, II, IV, V). HCO3– act differently as with
an increase of catchment area, their share in chemical composition of water increases (profile II). SO42– act
irregularly as both their increase and decrease in the chemical composition of water can be observed (see: Fig. 2).
Seasonal changes in the structure of the chemical composition of waters
Analysis of seasonal changes in the share of ions in the chemical composition of water shows no changes expressed in hydrochemical types of water for most catchments (n = 12). In four catchments, one change of hydrochemical type of water was observed in a year and several changes in catchment no. 2 – the most de-forested one. In catchment no. 2, chemical composi-tion of water is more complex in winter and spring – four–ion waters SO4–[NO3]–Ca–Mg, while in
sum-mer and autumn more diverse hydrochemical types of water can be observed: two–ion waters SO4–Ca and three–ion waters: SO4–[NO3]–Ca, SO4–Ca–Mg (see: Table 5).
Analysing changes in the share of NO3– in the
chem-ical composition of water during the year, the changes observed were in line with expectations and opposite to expected. In most catchments (1, 2, 5, 6, 7, 8, 12, 13, 14, 17), a bigger share of NO3– in the chemical
compo-sition of water was observed in winter, while a smaller one in summer (see: Fig. 3). It is associated with the accumulation of nitrogen by plants during the growing season. At the time, the concentration of NO3– in waters
decreases and their share in the chemical composition of water also decreases. A different phenomenon was observed in some heavily forested catchments (3, 9, 10) – in summer there was more NO3– in the chemical
composition of water, while in winter there was less (see: Fig. 3). This may indicate a continuous break-down of the forest stand in the catchment of the Ma-linowski stream. In some catchments (4, 11, 15, 16), no clearly oriented changes can be observed.
Analysing the variability of NO3– expressed with
the variability coefficient, it was observed that it is mostly moderate (in nine catchments). The remaining, extreme types – equalised and non–equalised – occur each of four. Diversity of types shows that the forest
Table 4.
The share of ions in the chemical composition of water
[% mval
· dm
–3] and coefficient of variation (Cv) in stream water (n = 12)
Forest zones ID Ca 2+ Mg 2+ Na + K + HCO 3 – SO 4 2– NO 3 – Cl – Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv Min. Avg. Max. Cv [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] [% mval · dm –3] [%] Upper 1 34.96 36.09 37.30 2.0 6.18 6.55 6.94 3.0 5.33 5.87 7.15 7.6 0.40 1.40 2.78 49.6 10.99 14.52 17.08 11.3 17.99 20.06 21.96 6.2 10.43 12.34 14.70 9.4 1.79 2.89 3.66 18.7 2 27.44 28.76 29.43 1.9 9.76 10.14 10.68 2.3 7.86 8.38 8.66 3.0 1.92 2.43 4.38 26.3 2.54 5.16 9.38 43.9 28.0 31.58 34.2 6.4 8.87 10.54 12.92 13.3 1.65 2.56 3.04 16.9 3 34.05 35.32 36.16 1.8 6.85 7.18 7.57 2.5 5.44 5.72 6.10 3.3 0.95 1.61 2.75 34.6 18.94 23.05 27.74 11.1 15.39 18.58 21.09 8.9 4.55 5.68 6.98 14.0 1.57 2.48 2.98 17.9 4 33.81 34.36 34.82 0.9 9.12 9.42 9.86 2.5 4.80 4.96 5.23 2.8 1.06 1.23 1.53 9.1 21.53 23.62 26.86 7.0 11.84 12.67 13.31 3.1 9.59 12.18 14.12 10.5 0.83 1.38 1.68 20.1 Average value 32.57 33.63 34.43 1.7 7.98 8.32 8.76 2.6 5.86 6.23 6.79 4.2 1.08 1.67 2.86 20.9 13.50 16.59 20.27 18.3 18.31 20.72 22.64 6.2 8.36 10.19 12.20 11.8 1.46 2.33 2.84 18.4 Middle 5 34.79 37.08 37.80 2.4 7.25 7.49 8.24 3.5 3.88 4.29 5.75 11.9 0.93 1.10 1.81 23.1 24.80 27.67 32.00 7.1 11.31 12.92 13.75 6.0 5.69 7.89 10.22 16.7 0.84 1.38 2.22 25.9 6 33.75 35.13 37.35 2.4 7.49 8.09 8.40 2.8 4.13 5.54 6.32 9.3 1.01 1.18 1.58 13.0 26.69 28.36 31.99 6.1 12.07 13.67 15.1 1 7.3 4.49 6.03 9.44 20.1 1.12 1.80 2.45 19.4 7 35.71 36.41 36.79 0.9 7.59 7.73 7.96 1.4 4.53 4.74 5.13 3.9 1.01 1.09 1.20 4.6 27.63 29.56 32.13 4.4 12.54 14.12 15.37 5.6 4.02 4.82 5.35 7.8 0.80 1.34 1.80 20.9 8 34.77 35.36 36.71 1.6 7.62 8.10 8.44 2.7 4.56 5.15 5.51 5.8 1.08 1.35 1.82 12.8 26.03 28.66 31.98 6.4 13.64 16.09 17.73 8.3 2.84 3.50 4.74 17.8 0.98 1.57 2.02 21.4 9 34.18 34.82 35.60 1.2 8.05 8.37 8.72 2.3 5.02 5.42 5.74 3.9 1.25 1.35 1.60 6.4 23.05 24.51 26.59 4.6 13.71 14.98 16.50 5.9 6.88 8.25 9.49 11.9 1.84 2.07 2.31 6.4 10 34.01 34.61 35.38 1.2 8.07 8.27 8.58 2.2 5.01 5.49 5.98 4.6 1.48 1.60 1.80 5.1 28.06 31.16 34.12 5.7 11.52 14.00 16.20 10.8 1.44 2.00 3.05 20.9 2.09 2.68 3.37 13.2 Average value 34.54 35.57 36.61 1.6 7.68 8.01 8.39 2.5 4.52 5.1 1 5.74 6.6 1.13 1.28 1.64 10.8 26.04 28.32 31.47 5.7 12.47 14.30 15.78 7.3 4.23 5.42 7.05 15.9 1.28 1.81 2.36 17.9 Lower 11 32.91 33.67 34.62 1.5 8.65 8.92 9.20 1.7 5.33 6.02 6.72 7.7 1.1 1 1.35 1.50 9.7 26.62 29.38 32.71 6.5 12.97 15.60 18.01 8.4 2.28 3.08 4.72 20.1 0.96 1.78 2.52 27.4 12 34.91 36.05 36.74 1.3 7.58 7.79 8.05 1.7 4.63 4.97 5.60 5.4 0.99 1.12 1.56 13.6 26.08 28.19 31.90 6.3 11.71 13.37 14.65 6.5 5.22 6.75 7.85 10.7 0.99 1.55 2.26 22.2 13 35.08 36.01 36.66 1.4 7.63 7.78 7.93 1.3 3.97 4.80 5.1 1 6.1 1.02 1.32 2.53 33.5 26.63 29.58 35.89 8.3 9.72 13.89 16.05 12.0 2.64 4.94 6.21 23.1 0.92 1.44 1.73 15.8 14 32.85 35.49 36.42 2.9 7.39 7.90 8.56 3.6 3.95 5.04 6.28 10.6 1.08 1.39 2.53 35.9 26.42 29.84 36.25 8.4 9.75 14.14 16.59 12.1 2.60 4.22 4.92 14.8 0.92 1.57 2.48 24.8 15 31.96 35.40 36.20 3.2 6.95 7.93 8.85 5.3 4.78 5.07 5.46 3.9 1.09 1.46 3.12 39.3 26.29 28.79 31.67 5.4 12.97 14.47 16.14 7.3 3.48 4.89 5.58 11.9 1.09 1.70 2.15 15.6 16 35.00 35.54 36.12 0.9 7.74 7.98 8.26 1.9 4.86 5.17 5.40 3.0 1.16 1.28 1.62 11.5 27.27 29.13 31.49 5.0 12.70 14.33 15.71 7.0 4.02 4.67 5.22 8.5 1.07 1.73 2.25 18.5 Mali- nowski 17 34.05 34.55 35.34 1.1 8.20 8.45 8.71 1.7 5.16 5.65 6.05 4.4 1.19 1.32 1.41 4.7 26.95 29.46 32.42 6.3 12.36 14.86 16.77 8.5 3.15 3.76 4.64 10.9 1.06 1.77 2.39 21.2 Average value 33.82 35.24 36.01 1.8 7.73 8.1 1 8.51 2.5 4.67 5.25 5.80 5.9 1.09 1.32 2.04 21.2 26.61 29.20 33.19 6.6 11.74 14.38 16.27 8.8 3.34 4.62 5.59 14.3 1.00 1.65 2.25 20.8
Table 5. Hydrochemical types of water in the Malinowski stream catchment
Seasons Winter Spring Summer Autumn Hydrochemical type
Forest zones ID XI XII I II III IV V VI VII VIII IX X
HCO 3 –SO 4 –Ca HCO 3 –Ca HCO 3 –SO 4 –[NO 3 ]–Ca SO4 –[NO 3 ]–Ca–Mg SO4 –[NO 3 ]–Ca SO4 –Ca–Mg SO–Ca4 Upper 1 12 2 6 1 3 2 3 12 4 1 11 Middle 5 11 1 6 12 7 12 8 12 9 12 10 12 Lower 11 12 12 12 13 11 1 14 11 1 15 12 16 12 17 12 Hydrochemical type
HCO3–SO4–Ca 9 8 9 9 9 9 9 9 8 9 9 9
HCO3–Ca 2
HCO3–SO4–[NO3]–Ca 2 3 2 2 2 2 2 2 1 2 2 2
SO4–[NO3]–Ca–Mg 1 1 1 1 1 1
SO4–[NO3]–Ca 1
SO4–Ca–Mg 1 1 1
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
106 www.acta.urk.edu.pl/pl
Fig. 2. Longitudinal hydrochemical profiles (I, II, III, IV, V, VI) in the Malinowski stream catchment (1–17 numbers of sub-catchments)
stand in the Malinowski stream catchment continu-ously breaks down. It is worth noticing that in defor-ested catchments, the variability of NO3– in a year is
higher (Cv = 13.3%; catchment no. 2) than in forested catchments (Cv = 9.4%; catchment no. 1) (see: Ta-ble 4). Deforested catchments are characterised most-ly by moderate type, while forested ones: moderate and equalised. The most significant changes occur in
catchments in which degradation of the forest stand (3, 9, 10) or its reconstruction (no. 4 – covered by young forest) can be observed.
SUMMARY AND DISCUSSION
The consequence of deforestation of the slopes in the Silesian Beskid range is a change of the sequence of anions in the chemical composition of water, which is reflected in the hydrochemical types of waters, which are their synthetic image. Share of SO42– ions in the
chemical composition of water in a stream that drains a catchment that is almost totally deforested (no. 2) was so significant that it was in the first place in this water’s hydrochemical type: SO4–[NO3]–Ca–Mg,
SO4–Ca–Mg, SO4–Ca, and SO4–[NO3]–Ca.
Mean-while, the concentration of HCO3– ions was so low that
their share in the chemical composition of water was minimal. Analogous hydrochemical environments in which SO42– dominated over HCO
3– were described by
Michalik (2008) and Michalik et al. (2012) in waters draining quartzite sandstones in the Świętokrzyskie Mountains, and by Kosmowska et al. (2015) and (2018) in the Malinowski stream catchment in the Silesian Beskid range. In the above catchments, the occurrence of SO42– in the first place in the
hydrochem-ical type of water is extremely rare for natural waters, especially since the Godula sandstones, that are the geological base of the above catchments, cannot be their source and the origin of SO42– must be
anthropo-genic. In the Tatras, Wolanin et al. (2017) described an unusual chemical composition of a spring, that was dominated by SO42– (28.12% mval ∙ dm–3) but it was
probably genetically connected to gypsum or anhy-drite rocks. A significant, and sometimes dominant, share of SO42– in the chemical composition of water
is associated with atmospheric supply of pollutants in the second half of the 20th century. It resulted in SO42– accumulation in the residual soil, and now they
are leached from the soil, which was discussed by Jasik and Małek (2013), Kosmowska et al. (2016) and (2018). In the waters draining the lower zone of the Skrzyczne massif and at the closing profile of the Ma-linowski stream catchment in Lipowa, a sequence of anions can be observed in the chemical composition of water that is typical for waters draining sedimentary rocks in the temperate climate, which is dominated by
Fig. 3. The course of NO3– regime [% mval ∙ dm–3] in
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
108 www.acta.urk.edu.pl/pl
HCO3–, with a smaller share of SO42–, Cl– and NO3–. It
can be observed in the hydrochemical type of water in which HCO3– are in the first place: HCO
3–SO4–Ca.
This kind of ion sequence, in which HCO3– dominate
and are in the first place, was obtained by Drużkow-ski and Szczepanowicz (1988) in a small catchment called Wierzbanówka in the Carpathian Foothills, Maultz (1972) in big catchments of the upper Wisła (Soła, Skawa), Welc (1985) in the catchment of the Bystrzanka stream, Żelazny (1995) and (2005) in catchments in the Wiśnicz Foothills, Siwek (2012) in small catchments at Carpatian Foothills (catchments of Stara Rzeka, Kubaleniec and Leśny Potok), Żelazny et al. (2017a) and (2017b) in the Kościeliski stream catchment in the Tatras. Also, research conducted in the Kościeliska valley in the Western Tatras confirm it (Żelazny et al., 2013; Kosmowska et al., 2018), as well as several years of observations of 23 streams in the Polish Tatras where Żelazny (2012) showed that HCO3– dominates among anions in the chemical
com-position of water regardless of hydrometeorological and lithological conditions. It is worth mentioning that in the Tatra catchments the mineralisation of water was strongly differentiated depending on the litholog-ical structure. In the waters of streams draining catch-ments built up low–soluble granites, mineralisation was very low (avg. = 17.70 mg ∙ dm–3 in the Roztoka
catchment), while in catchments built up sedimentary rocks it was much higher (avg. = 301.45 mg ∙ dm–3 in
the Wielkie Koryciska catchment) (Żelazny, 2012). Multidimensional PCA analysis carried out for wa-ters that drain the Malinowski stream catchment did not show the expected seasonal variability of biogenes concentration, e.g. NO3–, i.e. higher in winter, and
lower in summer (Kosmowska, 2016). However, the analysis of seasonal variability in the course of NO3–
concentration in waters from individual sub-catch-ments (% mval ∙ dm–3) showed typical variability. It
is worth noting that among these catchments, also an unusual phenomenon was observed – in summer there is a higher concentration of NO3– than in winter
(catchments no. 3, 9, 10). This should be explained by the intensive degradation of the forest stand in these catchments. This applies to catchments heav-ily transformed due to anthropopressure. According to Vitousek and Reiners (1975), Murdoch and Stod-dard (1992), Swank and Vose (1997) this indicates a
progressive degradation of the damaged forest stand, which behaves similarly to an aging forest stand and with time loses the ability to actively absorb NO3– in
the growing season. Vitousek and Reiners (1975) showed a multiple difference between NO3–
concen-tration in streams draining successional forest catch-ments (about Avg. = 5 μEQ ∙ dm–3
July 1973) and oldeged
forest catchments (about Arg. = 55 μEQ ∙ dm–3
July 1973).
For most catchments located in the middle and low-er zones of the Skrzyczne massif, a typical course of NO3– concentration was observed – higher
concentra-tion in winter, and lower in summer. Similar results – NO3– concentration increase in non–growing period,
and decrease in growing period – were obtained in the Tatras by Żelazny (2012), Wolanin (2013), Gromadz-ka et al. (2015), Sajdak et al. (2018), in the Babia Góra National Park by Malata (2015), in the Gorce range by Jasik et al. (2017), in the Silesian Beskid and the Żywiec Beskid by Astel et al. (2008), as well as in small agricultural catchments in the Lower Silesia by Pulikowski et al. (2005) and (2011). Similar seasonal variation in NO3– was observed in a small urbanised
catchment in England by Worrall and Burt (1998) and in the UK by Jarvie et al. (2010).
Analysing the changes in the hydrochemical types of waters along the longitudinal profiles in the Ma-linowski stream catchment, attention should be paid to the differences expressed in hydrochemical types in the chemical composition of the water draining the deforested upper zone of the Skrzyczne massif in comparison to the lower zone. As the catchment area increases, the share of NO3– in the chemical
compo-sition of water decreases, and the share of HCO3–
in-creases. Unique hydrochemical types of waters that drain the upper zone of the Skrzyczne massif (catch-ment no. 2) – SO4–[NO3]–Ca–Mg, SO4–Ca–Mg, SO4–
Ca, and SO4–[NO3]–Ca – are the result of the forest
stand degradation. Also, the methodological aspect related to the analysis of longitudinal hydrochemical profiles is important. The analysis of the ion share in the chemical composition of water that was carried out in the longitudinal hydrochemical profiles allows the identification of the hydrochemical effects of the degradation of the forest stand in the mountain catch-ment. It is worth noting that if the tests were carried out exclusively in the closing profile of the Malinows-ki stream catchment in Lipowa, then this catchment
would be a typical Carpathian catchment in terms of hydrochemistry, where HCO3– is in the first place in the
anionic part of the chemical composition. This would “mask” the impact of anthropogenic influence on the hydrochemical functioning of the catchment.
ACKNOWLEDGEMENTS
The research was conducted within the 2011/01/B/ NZ9/04615 grant by the National Science Centre – „The impact of deforestation caused by ecological disaster on the spatial variation and changes in the chemistry of source and surface waters in the Silesian Beskid.”
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WPŁYW WYLESIENIA NA ZMIANY UDZIAŁU JONÓW W SKŁADZIE CHEMICZNYM WÓD MALINOWSKIEGO POTOKU WZDŁUŻ PODŁUŻNYCH PROFILI HYDROCHEMICZNYCH
ABSTRAKT Cel pracy
Celem badań było określenie zmian udziału jonów w składzie chemicznym wody wraz z przyrostem po-wierzchni zlewni wzdłuż podłużnych profili hydrochemicznych na obszarze dotkniętym klęską ekologiczną. Materiał i metody
Badania prowadzono w zlewni Malinowskiego Potoku w Masywie Skrzyczne w Beskidzie Śląskim, w latach 2013–2014. Zlewnię Malinowskiego Potoku podzielono na mniejsze zlewnie cząstkowe: zależne i niezależ-ne oraz wyodrębniono 6 profili podłużnych wzdłuż zlewni wraz z przyrostem powierzchni zlewni. W terenie pobierano co miesiąc próbki wody w zlewniach o różnym stopniu wylesienia oraz mierzono cechy
fizycz-no-chemiczne wody (pH, EC25°C, Tw). W laboratorium metodą chromatografii jonowej (DIONEX 2000)
oznaczono skład chemiczny wód w zakresie 14 jonów (Ca2+, Mg2+, Na+, K+, NH
4+, Li+, HCO3–, SO42–, Cl–,
NO2–, NO3–, PO43–, Br–, F–).
Wyniki i wnioski
Przeprowadzone badania wykazały wpływ wylesienia na udział jonów w składzie chemicznym wody.
W zlewniach wylesionych zaobserwowano wzrost udziału SO42– i spadek HCO3–. Udział SO42– w wodach
odwadniających zlewnię wylesioną był tak duży, że pojawił się na pierwszym miejscu w typie
Kosmowska, A. (2019). Impact of deforestation on changes of ion share in chemical composition of waters of the Malinowski stream along longitudinal... Acta Sci. Pol., Formatio Circumiectus, 18 (3), 97–112. DOI: http://dx.doi.org/10.15576/ASP.FC/2019.18.3.97
112 www.acta.urk.edu.pl/pl
hydrochemicznych wzdłuż profili podłużnych, zauważono odmienność składu chemicznego wód odwadnia-jących górną, wylesioną strefę, w porównaniu do dolnej. Wraz z przyrostem powierzchni zlewni, następuje
spadek znaczenia NO3– i wzrost znaczenia HCO3–. Gdyby badania prowadzono jedynie w profilu
zamykają-cym zlewnią Malinowskiego Potoku, wówczas zlewnia ta byłaby typową zlewnią karpacką pod względem hydrochemicznym, gdzie na pierwszym miejscu w składzie chemicznym wody występują wodorowęglany. Analiza składu chemicznego wód przeprowadzona w podłużnych profilach pozwala zidentyfikować hydro-chemiczne skutki rozpadu drzewostanu w zlewni górskiej.
